1

Supporting Information

Crystalline and permanently porous porphyrin-based metal

tetraphosphonates

Timo Rhauderwiek,a Konrad Wolkersdörfer,b Sigurd Øien-Ødegaard,c Karl-Petter Lillerud,c Michael Warkb and

Norbert Stocka,c

a Institute of Inorganic Chemistry, Christian-Albrechts-Universität, Max-Eyth Straße 2,

D-24118 Kiel, Germany.

b Chemical Technology 1, Carl von Ossietzky University Oldenburg, Carl-von-Ossietzky Str.

9-11, D-26129 Oldenburg, Germany.

c Department of Chemistry, University of Oslo, Sem Sælands vei 26, N-0371 Oslo, Norway.

1. Materials and Characterization……………………………………..………………..2-3

2. Synthesis of Ni-H8TPPP and M-CAU-29 (M= Mn, Co, Ni, Cd). ………………..….4-8

3. SEM image of Ni-CAU-29, coordination mode, crystallographic parameters, bond

distances and results of the Rietveld- and Pawley refinement of M-CAU-29….....9-14

4. H2O Sorption properties and PXRD patterns of the activated samples ……………15

5. TG investigations, PXRD patterns of the decomposition products, VT-PXRD studies

and chemical stability.………………………………………………………………16-21

6. Proton conductivity…...…………………………………………………………….22-27

7. IR and UV/vis spectroscopy ………………………………………………………..28-29

8. References……………………………………………………………………………….30

Electronic Supplementary Material (ESI) for ChemComm.This journal is © The Royal Society of Chemistry 2017

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1 Materials and Characterization

1.1 Materials. MnCl2 ∙ 4 H2O (99 %, Merck), CoCl2 ∙ 6 H2O (98 %, Fluka), NiCl2 ∙ 6 H2O (97 %, Merck), CdCl2 ∙ H2O (98 %, Merck), EtOH (99 % + 1 % MEK, Walther), dichloromethane (Walther), N,N-diemthylformamide (99 %, Grüssing), acetone (99 %, Walther), 100 % acetic acid (VWR chemicals), NaH2PO4 (99 %, Sigma-Aldrich) and Na2HPO4 (99 %, Sigma-Aldrich) were used without further purification. The linker Ni-4,4',4'',4'''-(5,10,15,20-porphyrintetrayl)tetraphosphonobenzoic acid Ni-(4-tetraphosphonophenylporphyrin, Ni-H8TPPP) was synthesized according to reported procedures1-3 starting with 4-bromobenzaldehyd (98 %, ABCR) and pyrrole (98 %, ABCR) in propionic acid (99 %, Grüssing) with following NiCl2-catalyzed (97 %, Merck) phosphonylation in 1,3-Diisopropylbenzene (96 %, Sigma-Aldrich) using triethyl phosphite (98 %, Sigma-Aldrich) with following hydrolysis in conc. HCl (35 %, VWR chemicals). Details are given in the Supporting Information.

1.2 Characterization.Single crystal X-ray diffraction data for Ni-CAU-29 were acquired using a Bruker D8 Venture diffractometer equipped with a Photon 100 CMOS area detector and a Mo Kα microsource (λ = 0.71073 Å). The reflections were indexed with the APEX3 suite, integrated with SAINT V9.32B,4 solved with the program SHELXT,5 and refined with the program SHELXL using Olex2 as GUI.6 The crystal was very small (5 x 20 µm) and poorly diffracting, limiting the resolution to a (sin θ)/λ value of 0.36 which corresponds to a d spacing of 1.4 Å. The data also showed poor consistency (Rint = 0.186). The poor diffraction at higher angles resulted in a low number of unique reflections and thus limited accuracy of determined bond lengths. Geometric constraints were used on the 6-membered rings in the structure refinement to improve the data-to-parameter ratio, although the structure refines just as well without.The structure contains sheets of stacked porphyrin rings, likely to cause stacking disorder in the crystals. This disorder is likely to have caused the poor diffraction quality, thus resulting in low precision on bond lengths and ADP values in the obtained crystal structures. Only Ni and P atoms were refined anisotropically to avoid overparametrization.The crystal structure contains 1-dimensional channels along [1 0 0] that are partly filled with an unknown adsorbate. The data quality is not sufficient to use solvent masking. Instead, dummy atoms (C47, C48, O14) were used to emulate adsorbed species at the points of highest electron density in the pores (obtained from the Fourier difference map). High resolution PXRD patterns were measured on a STOE Stadi-P combi powder diffractometer equipped with a Mythen detector (Cu K 1 radiation). Rietveld-refinements and 𝛼Pawley-fits (Fig. S8 – S11) were carried out for all M-CAU-29 (M= Mn, Co, Ni, Cd) derivatives to proof that they are phase pure and isostructural to Ni-CAU-29. Pawley-fits were performed with the program TOPAS academic V4.1.7 The results of the refinement and crystallographic data of M-CAU-29 is shown in Table S2. The diameters of all pores were determined using DIAMOND V.38 taking the van-der-Waals radii of the atoms into account as well as Material Studio V5 9 to determine the Connolly surface. The VT-PXRD measurements were recorded on a STOE Stadi-P combi powder diffractometer (Mo K 1 radiation) equipped with a capillary 𝛼furnace. For the measurements 0.5 mm quartz capillaries were used. The samples were heated up in steps of 5 K between 25 and 450 °C and measured for 10 minutes each. IR-spectra were recorded using a Bruker ALPHA-FT-IR A220/D-01 spectrometer equipped with an ATR-unit. UV/vis spectra were recorded at a Spectroquant Pharo 300 M. Prior to the measurements all samples were dissolved in 2M NaOH and measured at once. The 1H- and 31P-

3

NMR spectra of the Ni-H8TPPP linker were recorded on a Bruker DRX 500 spectrometer. Sorption experiments were performed with a BEL Japan Inc. BELSORP-max. Before sorption measurements all samples were activated at 170 °C under reduced pressure (10-2 kPa) for 16 h. Thermogravimetric measurements were performed on a NETZSCH STA 409 CD analyzer under a flow of air (75 ml min-1) with a heating rate of 4 °C min-1 between 25 and 700 °C in Al2O3-crucibles. The data were corrected for buoyancy and current effects.

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2. Synthesis of Ni-H8TPPP and M-CAU-29 (M= Mn, Co, Ni, Cd).

The three step synthesis route of Ni-H8TCPP (Fig. S1) was carried out employing in the first step the Adler method1, 2 in the synthesis of 4-Bromophenylporphyrin (H2TBrPP). The second step, the phosphorylation of H2TBrPP was achieved by using a Ni-catalyzed variation of the Arbuzov reaction,3, 10 with the following third step, the hydrolysis of the -PO(OEt)2 groups in conc. HCl.

Figure S1. Schematic representation of the synthesis route of Ni-H8TPPP.

H2TBrPP: Pyrrole (7.47 mL, 108 mmol) and 4-brombenzaldehyde (20.0 g, 108 mmol) in 400 mL propionic acid were heated under reflux for 2 h. Afterwards the reaction mixture was cooled down to room temperature and poured into 500 mL of MeOH and stirred for 30 min in an ice bath. The resulting precipitate was filtered off and washed several times with MeOH until the filtrate was clear. Subsequently, the product was washed with 100 mL warm distilled water and dried at 70 °C in a drying oven over night. A blue powder of H2TBrPP 7.63 g (8.2 mmol, 30.4 %) was obtained.

Elemental analysis of H2TBrPP (Br4C44H26N4): calc (%): C 56.8, H 2.6, N 6.0, found (%): C 59.7, H 3.2, N 6.2. The small difference between the calculated and observed values is due to impurities caused by propionic acid used in the synthesis. Propionic acid was also observed in the 1H-NMR measurements, but not in the 1H-NMR spectra of the products in the next synthesis steps. The low intensity peaks between 8.5 and 8.0 ppm are due to interactions of the H2TBrPP with propionic acid, indicated by the different chemical shift and have no influence on the purity of the products in the next synthesis steps.

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1H-NMR (Fig. S2), H2TBrPP (500 MHz CDCl3): δ= 8.76 (s, 8H, H-1); 7.99 (d, 8H, H-2); 7.82 (d, 8H, H-3); 7.18 (s, 1H, CDCl3); 2.30 (q, 2H, propionic acid); 1.08 (t, 3H, propionic acid) ppm. Additional peaks between 7 and 9 ppm are due to low impurities with higher condensated porphyrines.

Figure S2. 1H-NMR spectrum of H2TBrPP digested in DMSO.

Ni-H8TPPP: H2TBrPP (3.42 g, 3.7 mmol) and anhydrous NiCl2 (1.79 g, 13.8 mmol) in 70 mL 1,3-diisopropylbenzene (prior the reaction for 30 min with N2 degassed) were heated up to exactly 170 °C under N2 atmosphere. Afterwards triethylphosphite (7.05 mL, 43.7 mmol) as added slowly (30 min) and dropwise to the reaction mixture and heated for further 24 h at 170 °C. The reaction mixture was cooled down to room temperature and the resulting precipitate was filtered off and washed with 250 mL DCM. The resulting organic phase was washed 2 times each with 100 mL H2O. The organic solvents were evaporated under reduced pressure and the resulting precipitate was hydrolyzed with 80 mL conc. HCl at 110 °C over 72 h. The resulting product was filtered off, washed with 100 mL cooled water and afterwards stirred in 100 mL DCM for 24 h. The resulting clean product was filtered off and dried at 70 °C in a drying oven over night. A red powder of Ni-H8TPPP 2.74 g (2.76 mmol, 75 %) was obtained.

Elemental analysis of Ni-H8TPPP (C44H32N4NiO12) ∙ 4H2O: calc (%): C 49.8, H 3.6, N 5.3, found (%): C 49.1, H 3.6, N 5.1.

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1H-NMR (Abb. S3), Ni-H8TPPP (500 MHz DMSO-d6): δ= 8.74 (s, 8H, H-1); 8.11 (dd, 8H, H-2); 8.06 (dd, 8H, H-3); 2.50 (s, 6H, DMSO-d6); 2.09 (s, 6H, acetone) ppm.

Figure S3. 1H-NMR spectrum of Ni-H8TPPP digested in DMSO.

31P-NMR (Abb. S4), Ni-H8TPPP (500 MHz DMSO-d6): δ= 12.04 (s, 4P, -PO(OH)2) ppm.

Figure S4. 31P-NMR spectrum of Ni-H8TPPP digested in DMSO.

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Synthesis of M-CAU-29.High-throughput methods (2 mL teflon inserts) were employed in the screening of synthesis parameters such as molar ratio of metal to linker, pH and reaction temperature. The usage of molar linker to metal ratios of 1 : 1 resulted in CAU-29 with low crystallinity, while higher ratios up to a five times excess of metal (1 : 1 in the structure) and the 3-fold concentration of the reactants led to highly crystalline CAU-29 (Fig. S5). Furthermore an upscaling in 30 mL teflon inserts of CAU-29 was possible using the 12 fold amount of all reactants. In the following the optimized and upscaled synthesis parameters of M-CAU-29 (M= Mn, Co, Ni, Cd) are given.The usage of other divalent cations like Mg2+, Ca2+, Fe2+, Cu2+ and Zn2+ under this synthesis conditions led in most cases either to X-ray amorphous or products of low crystallinity.

Synthesis of Mn-CAU-29: Ni-H8TPPP (180 mg, 18.3 x 10-5 mmol), MnCl2 ∙ 4 H2O (190.5 mg, 91.5 x 10-5 mmol) and H2O (12 mL) were added to a 30 mL Teflon insert and placed in a steel reactor. The reactor was heated for 48 h at 180 °C and cooled down to room temperature in 6 h. The resulting product was filtered off and washed with H2O and acetone. A yield of 162 mg, (84 % based on Ni-H8TPPP) was obtained for Mn-CAU-29, [Mn(Ni-H6TPPP)(H2O)] ∙ 7 H2O. Elemental analysis of Mn-CAU-29: calc (%): C 50.4, H 4.2, N 5.4, found (%): C 50.1, H 3.4, N 5.2.

Synthesis of Co-CAU-29: Ni-H8TPPP (180 mg, 18.3 x 10-5 mmol), CoCl2 ∙ 6 H2O (229.2 mg, 91.5 x 10-5 mmol) and H2O (12 mL) were added to a 30 mL Teflon insert and placed in a steel reactor. The reactor was heated for 48 h at 180 °C and cooled down to room temperature in 6 h. The resulting product was filtered off and washed with H2O and acetone. A yield of 156 mg, (81 % based on Ni-H8TPPP) was obtained for Co-CAU-29, [Co(Ni- H6TPPP)(H2O)] ∙ 5 H2O. Elemental analysis of Co-CAU-29: calc (%): C 49.2, H 3.8, N 5.2, found (%): C 49.3, H 3.3, N 5.1.

Synthesis of Ni-CAU-29: Ni-H8TPPP (180 mg, 18.3 x 10-5 mmol), NiCl2 ∙ 6 H2O (228.9 mg, 91.5 x 10-5 mmol) and H2O (12 mL) were added to a 30 mL Teflon insert and placed in a steel reactor. The reactor was heated for 48 h at 180 °C and cooled down to room temperature in 6 h. The resulting product was filtered off and washed with H2O and acetone. A yield of 165 mg, (86 % based on Ni-H8TPPP) was obtained for Ni-CAU-29, [Ni(Ni- H6TPPP)(H2O)] ∙ 5 H2O. Elemental analysis of Ni-CAU-29: calc (%): C 49.2, H 3.8, N 5.2, found (%): C 49.3, H 3.4, N 5.1.

Synthesis of Cd-CAU-29: Ni-H8TPPP (180 mg, 18.3 x 10-5 mmol), CdCl2 ∙ H2O (193.8 mg, 91.5 x 10-5 mmol) and H2O (12 mL) were added to a 30 mL Teflon insert and placed in a steel reactor. The reactor was heated for 48 h at 180 °C and cooled down to room temperature in 6 h. The resulting product was filtered off and washed with H2O and acetone. A yield of 180 mg, (89 % based on Ni-H8TPPP) was obtained for Cd-CAU-29, [Cd(Ni- H6TPPP)(H2O)] ∙ 7 H2O. Elemental analysis of Ni-CAU-29: calc (%): C 47.8, H 4.0, N 5.1, found (%): C 47.7, H 3.2, N 4.9.

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Figure S5. Results of the high-throughput investigation of CAU-29.

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3. SEM image of Ni-CAU-29, coordination mode, crystallographic parameters, bond distances and results of the Rietveld- and Pawley-refinement of M-CAU-29

The SEM image of Ni-CAU-29 reveals small needles and block shaped crystals in a range of 10-50 µm.The coordination mode of the (di)hydrogen phosphonate groups (P003-P006) in Ni-CAU-29 is given in Figure S7 using the Harris notation. The Harris-notation has the format [A,XYZ], the value A is the number of metal ions coordinated by the (di)hydrogen phosphonate group and X, Y, Z is the number of bonds every oxygen shares with a metal ion.11

The crystallographic data and results of the single crystal X-ray diffraction analysis of Ni-CAU-29 (Tab. S1, selected bond lengths Tab. S1a) and all M-CAU-29 derivatives (Tab. S2) reveal very similar cell parameters and the resulting Rietveld- and Pawley-refinements prove all M-CAU-29 (M=Mn, Co, Ni, Cd) derivatives are isostructural and show no further impurities in the samples (Fig. S8 – S11).

Figure S6. SEM image of Ni-CAU-29. The SEM measurements reveal crystal sizes between 10 and 50 µm.

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Figure S7. Graphical representation of the coordination mode of the (di)hydrogen phosphonate groups (P003-P006) in Ni-CAU-29. Numbers in brackets represent the Harris notation.

Table S1. Results of the single crystal X-ray diffraction analysis of Ni-CAU-29.Ni-CAU-29

Crystal system triclinica [Å]b [Å]c [Å]

9.561(5)15.086(9) 16.722(9)

α [°]β [°]γ [°]

94.723(9)97.602(9) 97.880(9)

V [Å3] 2356(2)Z 2

space group 𝑃1̅total data

unique dataRint

604018320.118

Observed data [I>2σ(I)] 1180R1 [I > 2σ(I)] [%]

wR2 [I > 2σ(I)] [%]9.97

a23.46GOF 1.13

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Table S1a. Selected bond lenghts in Ni-CAU-29.

bond distance [Å] bond distance [Å]

Ni01—O007 2.11 (2) P003—C00P 1.794 (18)

Ni01—O007 2.14 (2) P004—O009 1.50 (2)

Ni01—O008 2.05 (2) P004—O00A 1.57 (2)

Ni01—O009 2.13 (2) P004—O00B 1.52 (2)

Ni01—O00E 2.10 (2) P004—C01B 1.86 (2)

Ni01—O00F 2.04 (2) P005—O008 1.48 (2)

Ni02—N00H 1.90 (2) P005—O00G 1.57 (2)

Ni02—N00L 1.95 (3) P005—O00J 1.54 (2)

Ni02—N00M 1.94 (3) P005—C01E 1.78 (2)

Ni02—N00N 1.93 (3) P006—O00F 1.51 (2)

P003—O007 1.50 (2) P006—O00I 1.56 (3)

P003—O00C 1.55 (2) P006—O00K 1.56 (2)

P003—O00D 1.57 (2) P006—C01G 1.83 (2)

Rietveld refinements of Co- and Ni-CAU-29.

To further confirm the crystal structures of Ni- and Co-CAU-29, structure refinements by the Rietveld method were carried out using TOPAS academics V4.1.7 The structure as determined from single crystal X-ray diffraction was used as a starting point. The hydrogen atoms, guest atoms and atoms resulting from disorder were removed from the structure after inserting cobalt atoms into the inorganic building unit. The Ni-tetra(4-phosphonophenyl)porphyrin moiety was refined as rigid body while the positions of all other atoms were freely refined. Residual electron density was identified by Fourier synthesis and considered as two independent oxygen atoms, representing any kind of guest molecules, although the interatomic distances are in a reasonable range for strong hydrogen bonding. The temperature factors of the rigid body and all other atoms, respectively, were refined as general coefficients. In addition preferred orientation along the c axis was also taken into account. The structure obtained after convergence was further used as starting point for the Rietveld refinement of Ni-CAU-29 which was refined in the same manner. The final plots are shown below in Figure S9 and S10 and some relevant parameters are summarized in Table S2.

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Table S2. Results of the Rietveld refinements of Co- and Ni-CAU-29 and Pawley refinements of Mn- and Cd-CAU-29 of the crystallographic data of M-CAU-29 (M= Mn, Co, Ni, Cd).

Mn Co Ni CdSG P1̅ P1̅ P1̅ P1̅

a [Å]b [Å]c [Å]

9.761(2) 15.055(5) 17.022(6)

9.6860(7) 15.1223(18) 16.7747(22)

9.6473(6) 15.1046(15) 16.7115(19)

9.691(3) 15.067(7) 16.722(9)

α [°]β [°]γ [°]

94.168(7) 96.809(20) 97.057(17)

94.751(3) 97.412(8) 97.288(8)

94.662(4) 97.263(8) 97.309(7)

94.638(10) 97.158(35) 97.489(29)

V [Å3] 2455(1) 2404.5(5) 2384.3(4) 2390(2)GoF

Rwp [%]RBragg [%]

1.65 3.51

1.1 3.10.7

1.5 6.72.5

1.75 3.42

Figure S8. Result of the Pawley fit of Mn-CAU-29 (as-synthesized). Measured data are shown as a black line, calculated data as a red line and the blue line gives the difference plot. Predicted peak positions are marked as vertical bars.

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Figure 9: Result of the Rietveld refinement of Co-CAU-29. The black line gives the measured data, the red line gives the fit and the blue line is the difference curve. Black vertical bars indicate allowed peak positions.

Figure 10: Result of the Rietveld refinement of Ni-CAU-29. The black line gives the measured data, the red line gives the fit and the blue line is the difference curve. Black vertical bars indicate allowed peak positions.

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Figure S11. Result of the Pawley fit of Cd-CAU-29 (as-synthesized). Measured data are shown as a black line, calculated data as a red line and the blue line gives the difference plot. Predicted peak positions are marked as vertical bars.

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4. H2O Sorption properties and PXRD patterns of the activated samples

H2O-sorpton isotherms of M-CAU-29 (M= Mn, Co, Ni, Cd) (Figure S12) and PXRD patterns of the samples after the sorption experiment compared with the PXRD pattern before the measurement (Figure S13).

Figure S12. Results of the H2O sorption experiments at 298 K (activated prior measurement at 170 °C, overnight under reduced pressure of 10-2 kPa). The uptake corresponds to the amount of physisorbed water in the pores (Mn- : 9 H2O, Co- : 11 H2O, Ni- : 11 H2O, Cd- : 8 H2O).

Figure S13. PXRD patterns of M-CAU-29 (M= Mn, Co, Ni, Cd) after the sorption experiments (activation 170 °C, 10-2 kPa). For comparison the patterns of M-CAU-29 before the sorption experiment are also presented below the ones after the sorption experiments each.

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5. TG investigations, PXRD patterns of the decomposition products, VT-PXRD studies and chemical stability.

The results of all TG measurements are shown in Fig. S14-S18 and Tab. S3. The decomposition products of M-CAU-29 (M= Mn, Co, Ni, Cd) are Ni-M-pyro- and metaphosphates (M= Mn, Co, Cd) which was shown by PXRD measurements (Fig. S19). The results of VT-PXRD studies (Fig. S20- S23) confirm the results obtained from the TG measurements. Complete collapse of the frameworks takes place above ca. 350 °C.The results of the chemical stability test in different solvents as well as in a pH range between 0 and 14 and phosphate buffer (pH 7) are shown for Ni-CAU-29 in Fig. S24.

Table S3. Results of the TG measurements of M-CAU-29 (M=Mn, Co, Ni, Cd). Number in brackets represents the amount of H2O taken up during H2O sorption experiments.

sum formula residual mass meas. [%]calc. [%]

mass loss linker decomposition meas. [%]calc. [%]

mass loss H2O meas. [%]calc. [%]

[Mn(Ni-H6TPPP)(H2O)] ∙ 6.7 H2O (9.0 H2O)

31.131.8

58.959.4

8.88.8

[Co(Ni-H6TPPP)(H2O)] ∙ 6.4 H2O (11.2 H2O)

35.532.1

55.559.4

8.0 8.0

[Ni(Ni-H6TPPP)(H2O)] ∙ 9.0 H2O (10.8 H2O)

34.831.0

56.057.4

11.311.3

[Cd(Ni-H6TPPP)(H2O)] ∙ 8.2 H2O (7.9 H2O)

34.434.7

58.257.2

8.2 8.2

Figure S14. Thermogravimetric curve of Mn-CAU-29 (under air). Evaluation of the data reveals a molar ratio of metal : linker : H2O of 1 : 2.0 : 6.7 (Tab. S3). The weight gain before

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the collapse of the framework indicates a reaction for example between the Ni2+ ions with oxygen, since it was not observed in the TG measurement under N2 atmosphere.

Figure S15. Thermogravimetric curve of Co-CAU-29 (under air). Evaluation of the data reveals a molar ratio of metal : linker : H2O of 1 : 2.4 : 6.4 (Tab. S3). The weight gain before the collapse of the framework indicates a reaction for example between the Ni2+ ions with oxygen, since it was not observed in the TG measurement under N2 atmosphere.

Figure S16. Thermogravimetric curve of Ni-CAU-29 (under air). Evaluation of the data reveals a molar ratio of metal : linker : H2O of 1 : 2.3 : 9.0 (Tab. S3). The weight gain before the collapse of the framework indicates a reaction for example between the Ni2+ ions with oxygen, since it was not observed in the TG measurement under N2 atmosphere.

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Figure S17. Thermogravimetric curve of Ni-CAU-29 (under N2). Measurement under N2 could only be carried out up to a temperature of 800 °C. The whole curve is shifted to higher temperatures compared to the measurement under air, though the observed weight gain before the collapse of the framework is not observed anymore.

Figure S18. Thermogravimetric curve of Cd-CAU-29 (under air). Evaluation of the data reveals a molar ratio of metal : linker : H2O of 1.9 : 1 : 6.3 (Tab. S3). The weight gain before the collapse of the framework indicates a reaction for example between the Ni2+ ions with oxygen, since it was not observed in the TG measurement under N2 atmosphere.

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Figure S19. PXRD pattern of M-Ni-phosphates (M=Mn, Co, Ni, Cd) (ICSD-79015, 3000027, 27424, 35730, 81575) compared with the remaining products of the thermogravimetric experiments of M-CAU-29 (M= Mn, Co, Ni, Cd).

Figure 20. Results of the VT-PXRD studies of Mn-CAU-29 measured in open quartz capillaries (0.5 mm) under atmospheric conditions.

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Figure 21. Results of the VT-PXRD studies of Co-CAU-29 measured in open quartz capillaries (0.5 mm) under atmospheric conditions.

Figure 22. Results of the VT-PXRD studies of Ni-CAU-29 measured in open quartz capillaries (0.5 mm) under atmospheric conditions.

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Figure 23. Results of the VT-PXRD studies of Cd-CAU-29 measured in open quartz capillaries (0.5 mm) under atmospheric conditions.

Figure S24. Chemical stability of Ni-CAU-29 in different solvents (24 h, stirring at room temperature).

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6. Proton conductivity

The proton conductivity of Ni-CAU-29 was determined by electrochemical impedance spectroscopy (EIS). Powder samples were compressed between two porous stainless steel electrodes by a torque of 40 cN∙m to purchase pellets of 82 mm in diameter and approx. 0.53 mm thickness. GDL 25 BC (SGL) graphite felt ensures the connection of the pellet and the electrode surface. The Teflon sample holder was placed in a previously described custom-made measuring cell which was connected to a ZahnerZennium electrochemical workstation.12 In the EIS measurements an alternating voltage of 10 mV was employed in the frequency range from 1 Hz to 1 MHz. The relative humidity was adjusted by means of the temperature difference between sample chamber and water reservoir.

Figure S25a. Bode plots, top left: 50 % relative humidity, top right: 75 % relative humidity, bottom: 90 % relative humidity. Square symbols: ionic resistance, triangle symbols: phase shift.

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0 1x105 2x105 3x105 4x105 5x1050

1x105

2x105

3x105

4x105

5x105

Z'' [

]

Z' []

0.0 4.0x104 8.0x104 1.2x1050.0

2.0x104

4.0x104

6.0x104

8.0x104

1.0x105

1.2x105

Z'' [

]

Z' []

Figure S25b. Nyquist plots and equivalent circuit, top: equivalent circuit; bottom left: 50 % relative humidity, bottom right: 75 % relative humidity. Black: 80 °C, red: 100 °C, blue: 120 °C, green: 140 °C; square symbols: measured data, straight line: fits for the depicted equivalent circuit. The fits were computed with the program EIS Analyser 1.0.13

24

0 1x104 2x104 3x104 4x1040

1x104

2x104

3x104

4x104Z'

' [

]

Z' []

0 1x104 2x104 3x104 4x1040

1x104

2x104

3x104

4x104

Z'' [

]

Z' []

0 1x104 2x104 3x104 4x1040

1x104

2x104

3x104

4x104

Z'' [

]

Z' []

0 1x104 2x104 3x104 4x1040

1x104

2x104

3x104

4x104

Z'' [

]

Z' []

Figure S25c. Representative Nyquist plots for measurements at 90 %RH; square symbols: measured data, straight lines: fitted data. Clockwise: 80 °C, 100 °C, 120 °C, 140 °C.

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Figure S26. Comparison of the PXRD pattern of Ni-CAU-29 before and after the EIS measurements. Furthermore the PXRD pattern of the graphite felt in which the sample was embedded for the measurement is shown.

Table S4. Fit parameter.

relative humidity [%RH]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

temperature [°C]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

Parameters temperature [°C]

Parameters Values of the Parameters

Errors [%]

Values of the Parameters

temperature [°C]

Parameters Values of the Parameters

Errors [%]

Errors [%]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

R1 3.76E+05 0.16777P1 2.96E-10 0.84572n1 0.89067 0.10521P2 1.31E-05 2.4697

80

n2 0.202 6.1721R1 2.67E+05 0.8445P1 2.62E-10 2.0489n1 0.90695 0.21599P2 1.14E-05 1.6027

100

n2 0.20381 1.7565R1 1.39E+05 0.55092P1 1.99E-10 5.6562n1 0.94104 0.52788P2 8.29E-06 5.9269

120

n2 0.22955 4.8118R1 84191 0.41542P1 1.87E-10 2.797n1 0.94889 0.24101P2 8.67E-06 3.5874

50

140

n2 0.27614 1.7075

26

Relative humidity [%RH]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

temperature [°C]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

Parameters temperature [°C]

Parameters Values of the Parameters

Errors [%]

Values of thehe Parameters

temperature [°C]

Parameters Values of the Parameters

Errors [%]

Errors [%]

temperature [°C]

Parameters Values of the Parameters

Errors [%]

R1 70073 1.7805P1 2.46E-10 2.6283n1 0.92295 0.18929P2 2.45E-05 2.886

80

n2 0.32653 2.6006R1 53828 0.28282P1 2.99E-10 1.4666n1 0.90685 0.13069P2 3.36E-05 1.1611

100

n2 0.28825 1.5418R1 36602 0.30357P1 3.25E-10 1.6097n1 0.90064 0.13954P2 4.54E-05 1.1269

120

n2 0.26445 1.5289R1 26467 0.4174P1 3.07E-10 2.2488n1 0.90746 0.18776P2 5.86E-05 1.4152

75

140

n2 0.23732 1.9669R1 13661 3.0103P1 3.14E-10 1.2919n1 0.91296 0.10124P2 2.93E-05 1.146380n2 0.42224 1.5035R1 13359 0.19722P1 3.09E-10 3.377n1 0.90613 0.28191P2 4.35E-05 0.83672100n2 0.40667 0.44136R1 11512 1.2678P1 2.88E-10 4.8049n1 0.91297 0.36949P2 6.26E-05 1.2923120n2 0.39673 0.69649R1 10246 0.33638P1 2.31E-10 3.4176n1 0.93387 0.24437P2 8.25E-05 1.3766

90

140

n2 0.39097 0.87166

27

Figure S26. Comparison of the PXRD pattern of Ni-CAU-29 before and after the EIS measurements. Furthermore the PXRD pattern of the graphite felt in which the sample was embedded for the measurement is shown.

28

7. IR and UV/vis spectroscopy

IR spectra of M-CAU-29 (M= Mn, Co, Ni, Cd) and the Ni-H8TPPP linker are shown in Figures S27. The assignment of the bands are given in Table S4.

Figure S27. IR-spectra of M-CAU-29 (M= Mn, Co, Ni, Cd). For comparison the IR-spectrum of the linker Ni-H8TPPP (purple) is also presented.

Table S5. Assignment of the vibrations in the IR-spectra of M-CAU-29 (M= Mn, Co, Ni, Cd) and the free linker Ni-H8TPPP.14, 15

Vibration IR [cm-1]�̃� Mn Co Ni CdNi-H8TPPP

CH (phenyl, pyrrole)𝜈 2970 2970 2970 2970 2970 P-OH𝜈 1606 1606 1606 1606 1606 C=C (arom.)𝜈 1549 1549 1549 1549 1519 P-C (phenyl)𝜈 1480 1480 1480 1480 1480 C=C, N=C (in plane)𝛿 1389 1389 1389 1389 1389 C-N (pyrrole)𝜈 1352 1352 1352 1352 1352 P=O (stretching)𝜈 1223 1223 1223 1223 1223 P-O (stretching)𝜈 1136 1136 1136 1136 1136 C-H, N-H (pyrrole)𝛿 1100 1100 1100 1100 1100 C-H (in plane)𝛿 1005 1005 1005 1005 1005 P=O (stretching)𝜈 944 944 944 944 921 C-H (1,4-subst.)𝛾 793 793 793 793 793 C-H, N-H (pyrrole)𝛿 730 730 730 730 730 P-C 𝛾 704 704 704 704 704 P(OR)3𝛿 578 578 578 578 567 C=C (skeleton)𝛿 499 499 499 499 484

29

UV/vis spectra were recorded to prove the metalation of the porphyrin after the synthesis of the MOF (Fig. 28). For the measurement 0.1 mg sample was dissolved in 1 mL 2 M aqueous NaOH solution and filled up with water to a total volume of 5 mL. Afterwards a 4 mL cuvette was filled with 3 mL water and 5 drops of the porphyrin containing solution was added to the cuvette and subsequently measured.

Figure S28. UV/vis spectra between 380 and 800 nm of M-CAU-29 (M= Mn, Co, Ni, Cd) compared with the spectrum of the free linker Ni-H8TPPP (for comparison all intensities were normalized). All spectra show the absorption maximum (Soret-band) of the Nickel complexed porphyrin at 412/ 413 nm. Furthermore the Q1 band of the Ni complexed porphyrin is observed at 526/ 527 nm.

30

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